Sustain. Water Resour. Manag.
(2016) 2:183–197
DOI 10.1007/s40899-016-0050-y
ORIGINAL ARTICLE
Batch and column test analyses for hardness removal using
natural and homoionic clinoptilolite: breakthrough experiments
and modeling
Luvina Bibiano-Cruz1 • Jaime Garfias1 • Javier Salas-Garcı́a1 • Richard Martel2
Hilario Llanos3
Received: 18 September 2015 / Accepted: 13 March 2016 / Published online: 30 March 2016
Ó Springer International Publishing Switzerland 2016
Abstract Hard water causes many problems in domestic
and industrial usage, which has to be removed using cost-
effective technologies. To achieve this, the main goal of
this study is to assess and optimize the factors controlling
water softening applications. The research approach
included a combined use of batch and column experiments
performed in laboratory conditions through the ion
exchange process, evaluating the effectiveness of natural
and homoionic clinoptilolite on the removal characteristics
of divalent cations. The equilibrium data could be fitted by
both the Langmuir and the Freundlich models, even though
it was fitted better by the Langmuir model with a maximum
adsorption capacity of 10.5 mg g-1 for homoionic
clinoptilolite (HC) and 9.68 mg g-1 for the natural
clinoptilolite (NC). The adsorption kinetics can be suc-
cessfully fitted to pseudo-second order kinetic model and
the results of the intraparticle diffusion model suggest
intraparticle diffusion was not the only rate-controlling
step. It was also observed that the statistics indices of
agreements from non-linear Thomas model were higher
than that linear Thomas model. Nevertheless, the slope of
the breakthrough curve for the linearized method decreased
with increasing time as compared to non-linear method,
thereby resulting in a slightly steeper slope for the non-
linear method and reducing the adsorption capacity. The
& Jaime Garfias
jgarfiass@gmail.com
1
Faculty of Engineering (CIRA), Autonomous University
of the State of Mexico, C.P. 50130 Toluca, Mexico
2
Institut National de la Recherche Scientifique (INRS-ETE),
Québec, QC G1K 9A9, Canada
3
Departamento de Geodinámica, Universidad del Paı́s Vasco.,
Vitoria-Gasteiz, Spain
•
study also concludes that the non-linear method is slightly
more effective in predicting the performance of the selec-
tive removal efficiency of hardness ions. Results illustrate
that clinoptilolite may be used as an alternative to more
costly materials, due to its low cost and high abundance.
Keywords Hardness  Water softening  Clinoptilolite 
Ion exchange  Thomas model
Introduction
Purification of several contaminants in tap, ground, and
river water is needed for the drinking and industrial pur-
poses. Among the contaminants, hard water minerals such
as calcium, magnesium, iron, and manganese ions can react
with soap anions, decreasing the cleaning efficiency (Park
et al. 2007). The minerals also induce scaling problems and
serious failures in pipelines of boilers, heat exchangers, and
electrical appliances such as washing machines, dish-
washers and steam irons (Gabrielli et al. 2006).
To remove the divalent ions, several methods have been
widely applied as a means of effective water softening:
chemical precipitation, ion exchange process, nanofiltra-
tion, reverse osmosis, and electromembrane systems such
as electrodialysis, electrodialysis reversal, and electro-
deionization reversal. However, in case of the chemical
precipitation, the pH of water increased by adding the
alkaline additives and bicarbonates converted into car-
bonates as the precipitates. Due to the limited solubility of
calcium and magnesium salts (carbonates), the hardness of
water cannot be removed completely with this method
(Yildiz et al. 2003; Williams et al. 2002). In lime softening
method, this is limited by the solubility of calcite and
removal of carbonate hardness (Stumm and Morgan 1996).
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In membrane systems, monovalent ions and acids released
in the regeneration of membrane processes would result in
harmful effects on the environment. Finally, high power
consumption and expenses are required for operation and
maintenance of the equipment (Cuda et al. 2006; Gabrielli
et al. 2006; Ghizellaoui et al. 2005; Park et al. 2007). Thus,
a cost-effective and low energy consuming treatment pro-
cess has been forced on water softening process.
Ion exchange involves the replacement of ions adsorbed
on the surface of fine grained materials by ions in solution.
The most common use of this process is in domestic water
softening. Ion exchange processes have been shown to be
suitable for removal of hardness ions when this element is
in the ionized form (Helferrich 1962; Korngold et al. 2001;
Mohan and Pittman 2007). The main advantages with
respect to other alternative treatments are: high removal
efficiency, low chemical requirements and no modification
of drinking water organoleptic properties. In spite of its
advanced stage of development, various aspects of ion
exchange technology are being studied in many countries
to improve its efficiency and economy in its application to
hardness removal. Certain characteristics of ion exchange
materials and processes limit their applicability and
efficiency.
Although ion exchange materials have been used more
widely in practice (Rabideau et al. 2005; Han et al. 2007;
Chiavola et al. 2012), there still exist some problems: (1)
there is a crucial need for the development of a method that
is not only cost-effective and economic, but can also be
easily implemented. This led to a search for cheaper, easily
obtainable materials for the water softening; (2) although
the practical applications of hardness removal are generally
used in column mode, most research focuses on the batch
adsorption mode (Zou et al. 2011), so there is a lack of
research on the study of dynamic column methods. Natural
clinoptilolite (NC), as aluminosilicate mineral, has char-
acteristics of large surface area, strong capability of ions
exchange and adsorption for their particular tetrahedral
pore framework. Modeling of the ion exchange process can
also help in predicting the performance of the hardness
removal processes (Benefield et al. 1982; Chiavola et al.
2012). This can also support in evaluation of the technical-
economical feasibility of the ion exchange process as
compared to alternative systems. Therefore, systematic
investigations on the selective removal of divalent ions
using ion exchange processes are needed for water soft-
ening applications.
In view of the strategic importance of effective removal
efficiency of hardness ions, and the growing demands for
water of high quality for human consumption, the main
goal of this study is to assess and optimize the factors
controlling water softening applications, as well as evalu-
ating the effects of modifying the operating conditions. The
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Sustain. Water Resour. Manag. (2016) 2:183–197
research approach included a combined use of batch and
column experiments performed in laboratory conditions
through the ion exchange process, evaluating the effec-
tiveness of natural clinoptilolite (NC) and homoionic
clinoptilolite (HC) on the removal characteristics of diva-
lent cations. The obtained breakthrough curves were then
modeled and the values of the main constants of the best
fitting model determined. This allowed an examination of
performance assessment of a clinoptilolite treatment in
removing water hardness based on the assumption of
competitive cation-exchange as the dominant sorption
mechanism.
Materials and methods
To reduce water hardness, two laboratory procedures were
used to determinate the sorption clinoptilolite capacity for
hardness ions: batch (isotherms and kinetic models) and
column test experiments to obtain breakthrough profiles at
various contact times. The collected data were then
described using two modeling approaches, based on linear
and nonlinear analysis of the Thomas model, respectively.
The results of the modeling activity were then compared
with the results of column tests performed with synthetic
hard water (SHW), obtained with the same ionic concen-
tration as karstic spring water. Error analysis was carried
out to test the adequacy and accuracy of the model equa-
tions. The features of the different mathematical models
used to describe the results of the breakthrough experi-
ments are discussed in the following sections.
Synthetic inorganic surrogate of a natural hard
water sample
To perform experiments relevant to natural water, it can be
advantageous to use a medium with the same major ionic
composition as the natural water being studied, but without
natural constituents, such as trace components, colloids and
organic substances. In this study, the freshwater charac-
terization of a karst spring was selected to represent
chemical composition of natural hard water (NHW), which
was used as reference to prepare a synthetic hard water
(SHW) solution in the laboratory to test the affinity
between the sorbate and sorbent (Bibiano-Cruz 2009).
The selected natural hard water originates in a karstic
formation which is located in the Sierra Madre del Sur
province (600 masl), in the State of Guerrero, Mexico,
between 100°40 700 N and 18°210 5700 W. In this region, the
freshwater facies were characterized as Ca-HCO3-Cl,
enriched in some ions from dissolution of calcite-dolomite
and evaporite minerals (Bibiano-Cruz 2009). As a conse-
quence, calcium ions (Ca2?) contribute about 90 % of total
Sustain. Water Resour. Manag. (2016) 2:183–197
hardness; likewise the calcite oversaturation is due to CO2
outgassing in upwelling spring water.
The SHW solution was prepared according to generic
protocol for preparing synthetic freshwaters of desired
composition (Smith et al. 2002). This synthetic surrogate
emulates the major ion composition and ionic strength of
the water characterized (NHW). Most compositions
include Ca2?, Mg2?, Na? and K? cations and Cl-, SO42-,
NO3- and HCO- 3 anions. To avoid oversaturation and
precipitation in the SHW solution, the salts were arranged
in four groups to prevent incongruent solubility. The salts
used in the compatible stock solutions preparation were:
Solution A [CaCl26H2O ? Ca(NO3)24H2O], Solution B
[CaCO3], Solution C [KHCO3 ? KH2PO4 ? NaHCO3 ?
Na2SO4] and Solution D [MgSO47H2O]. To preserve
CaCO3 dissolution (Solution B), it was necessary to
increase the pCO2 during salt dissolution by vigorous
bubbling of CO2 gas for 10 min prior to the addition of the
CaCO3 powder, which was continued for 4 h to prevent
residual CaCO3 phase. Thus, the required concentrations of
each ion for each salt, as well as the mass of salt required to
make up an appropriate volume of each stock solution,
were considered to obtain the final volume of the SHW.
Accuracy of ion composition of the NHW was verified
by electroneutrality (EN) condition: EN (%) = (RCZ?
- RAZ-/RCZ? ? RAZ-) 9 100, where cations and
anions are expressed as meq L-1. The final SHW solution
was equilibrated by introducing atmospheric CO2 by
applying gentle air bubbling during 1 h. As a consequence,
the analytic composition of the SHW solution was ranged
with a margin of error of \1 %, taking into account
240 mg L-1 of total hardness as CaCO3, pH 6.5 ± 0.3 and
100 mg L-1 of CO2. In the SHW solution, the total hard-
ness is a measure of divalent cations and represents the
concentration of calcium (Ca2?) and magnesium (Mg2?)
ions, which correspond to the characterized properties of
the karstic system. In natural waters other polyvalent ions
also contribute to the hardness of water, but they are
generally present in much lower concentrations.
Ion exchange adsorbent
The raw zeolitic material used in this study was the natural
clinoptilolite (NC) that was taken from a sedimentary
deposit near of the Tehuacan region in the state of Puebla,
Mexico. This mineral was initially crushed and sieved to
recover the 2.4–4.8 mm size range to be used throughout
the experiments. In this schema, the clinoptilolite was
washed with distilled water several times, and dried in an
oven set at 100 °C and stabilized at room temperature to
obtain the natural clinoptilolite (NC) form.
To improve the clinoptilolite sorption capacity (Bibiano-
Cruz 2009), the natural clinoptilolite (NC) was pretreated
185
with 1 M NaCl for 24 h to obtain the homoionic clinop-
tilolite (HC) sodium form. The samples thus treated were
then washed in distilled water to remove any excess of
NaCl present on the surface, and dried in an oven set at
100 °C and stabilized at room temperature for 24 h. The
pretreatment of clinoptilolite was conducted based on the
findings of previous studies that alkali and alkaline earth
metals are cheap, commonly available and are the most
effective exchangeable ions for hardness removal
(Gorimbo et al. 2014).
Determination of exchange capacity
Batch contact time experiments
Sorption mechanisms depend on the sorbate-sorbent
interaction and the system conditions, therefore the
sorption capacity and required contact time were two of
the important parameters to determine. The bottle point
isotherm technique (Rivas et al. 2006) was employed to
determine the equilibrium capacity of the NC and HC for
hardness removal in the SHW solution. Batch sorption
experiments were conducted to determine the relationship
between adsorbent and adsorbate by varying the amounts
of adsorbate, both at equilibrium and as a function of
time.
The influence of adsorbent mass on the rate of hardness
sorption was determined by carrying out contact time
experiments using batch agitated reactor. Experimental
studies were conducted at room temperature (20 ± 1 °C)
by varying the adsorbent mass at the initially defined pH of
the SHW solution. Accordingly, experiments were carried
out in 250 ml flasks sealed by ParafilmÓ with varying
adsorbent mass from 0.5, 1, 3, 5, 10, 20 and 30 g mixed
with 200 ml of the SHW solution. In this context, the
samples were stirred continuously at 200 rpm (Big Bill
Digital Thermolyne shaker). Upon equilibration time
(24 h), the total hardness in the liquid phase was measured
and the absorbance accumulation on the adsorbent was
calculated via a mass balance.
To obtain the sorption capacity (Benguella and Benaissa
2002), the amount of hardness of the SHW adsorbed (qt)
per unit mass of clinoptilolite was calculated with the
following equation:
ðC0  Ct Þ  V
qt ¼ ; ð1Þ
W
where qt is the amount of hardness removed from the SHW
solution (mg g-1) at time t; C0 is the initial hardness
concentration of adsorbate (mg L-1); Ct is the equilibrium
concentration of hardness left in the solution after the
experiment (mg L-1); V is the solution volume (L), and
W is the weight of clinoptilolite (g).
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There are three isotherm models that have been widely
used to represent the response curves: namely linear,
Langmuir, and Freundlich models. The decision to select
the best model is based on the pattern of the sorption
curves. Adsorption isotherms describe the relationship
between the amount of adsorbed ion on adsorbent and the
final ion concentration in the solution. In this study, the
Langmuir (LG) (Eq. 2) and Freundlich (FR) (Eq. 3) iso-
therm models were tested to adequately correlate the
experimental data to find the best fit of the experimental
data. The parameters for FR and LG isotherms are very
useful for predicting adsorption capacities and also for
incorporating into mass transfer relationships in the design
of contacting equipment. The non-linear equation of
Langmuir isotherm model is expressed as follows.
qm bCe
qe ¼ ; ð2Þ
1 þ bCe
where Ce (mg L-1) and qe (mg g-1) are the concentration
of hardness ions in the liquid and solid phases, qm (mg g-1)
is the amount of solute adsorbed per unit weight adsorbent
in forming a complete monolayer on the surface, b
(L mg-1) is the constant related to the energy or net
enthalpy of adsorption intensity. The Freundlich isotherm
model is an empirical expression used in heterogeneous
systems and it is expressed as follows:
qe ¼ KF Ce1=n ; ð3Þ
-1 -1
where Ce (mg L ) and qe (mg g ) are the concentration of
hardness ions in the liquid and solid phases, KF (mg1-nLn-
g-1) is the adsorption coefficient and represents the adhesion
ability of the adsorbate onto the adsorbent (relative
adsorption capacity of the adsorbent), n (dimensionless) is
the adsorption equilibrium constant whose reciprocal is
indicative of adsorption intensity, respectively.
Kinetics of adsorption
To study the equilibrium time and adsorption rate, a series
of experiments were conducted to examine the adsorption
capacity of adsorbent mass using a SHW solution at con-
stant temperature (24 ± 1 °C). For the entire experiments,
1 g of a constant adsorbent mass was added to 100 ml of
the SHW solution in 250 ml flasks and placed on a shaker
at 200 rpm. The initial total hardness concentration of
SHW was 240 mg L-1 with a value of pH *6.5 ± 0.3. A
blank containing 100 ml of SHW solution without any
adsorbent was shaken simultaneously to determine any
adsorption process onto the walls of the flasks. The equi-
librium for the investigated systems was established for 5,
15, 30 and 60 min and then 3, 6, 12, 18 and 24 h. After
samples collection, the total hardness concentrations were
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Sustain. Water Resour. Manag. (2016) 2:183–197
determined with a FF-2 HACH test kit by titration method.
The experiment was performed in duplicate at room tem-
perature (20 °C).
The kinetic parameter study, which is helpful for the
prediction of adsorption rate, was performed based on
pseudo-first order, pseudo-second order and intraparticle
diffusion models, respectively. Lagergren first order model
(Eq. 4) is expressed by the following equation:
qt ¼ qe ð1  ek1 t Þ; ð4Þ
where k1 = Lagergren rate constant for adsorption (h-1),
qe = amount of ion adsorbed at equilibrium (mg g-1) and
qt = amount of ion adsorbed at any given time t (mg g-1).
According to Ho et al. (2000), the pseudo-second order is
described by the following equation:
k2 q2e t
qt ¼ ; ð5Þ
ð1 þ k2 qe tÞ
where k2 = pseudo-second order rate constant for adsorp-
tion (g mg-1 h-1), qe = amount of ion adsorbed at equi-
librium (mg g-1) and qt = amount of ion adsorbed at any
given time t (mg g-1). Data from batch experiments were
fitted to both models by nonlinear regression analysis using
software package SPSS v.13 for Windows (SPSS Inc.,
Chicago, USA).
The diffusivity of the solute molecules has an important
effect on the total rate of an adsorption process. Since the
pseudo-first and the pseudo-second order kinetic models
cannot identify the influence of diffusion on sorption, the
Weber and Morris equation was used for calculation of the
rate constants of intraparticle diffusion (Weber and Morris
1964). The intraparticle diffusion model presumes that film
diffusion or boundary layer diffusion is negligible, and that
intraparticle diffusion is the only rate-controlling step. The
rate of intraparticle diffusion can be calculated according to
the following equation:
qt ¼ Cd þ kd t1=2 ; ð6Þ
where kd is the intraparticle diffusion rate constant
(mmol g-1 min-0.5), and Cd is the intercept which is pro-
portional to the boundary layer thickness (mmol g-1). The
rate constant of intraparticle transport, kd, is estimated from
the slope of the linear portion of the plot of amount sorbed
against square root of time. In the case of a linear plot of qt
vs t0.5, and if the line passes through the origin, intra-
particle diffusion is the only rate-controlling step. If not,
some other mechanisms are also involved.
Column sorption studies
Although batch laboratory adsorption studies provide use-
ful data and parameters on the application of adsorbents for
Sustain. Water Resour. Manag. (2016) 2:183–197
hardness removal, the data obtained from batch adsorptive
system are not applicable to continuous adsorptive system,
thus continuous sorption studies are needed. Fixed-bed
column experiments were also necessary to provide prac-
tical operational information with respect to the adsorption
of constituents with the use of clinoptilolite as inorganic
ion exchangers.
Column studies were conducted using a PlexiglassÓ
column with an inner diameter of 5 cm and a length of
50 cm. Schematic details of the column test apparatus and
experimental column set-up is illustrated in Fig. 1,
including external components to estimate water softening
process. The column was completely filled for each test
with 1122.5 g of both NC and HC forms. The influent
concentration and flow rate of the SHW solution were keep
Fig. 1 Schematic details of the
column test apparatus and
experimental column set-up,
including external components
to estimate water softening
process
187
constants at 240 mg L-1 and 14 ml min-1, respectively.
Duplicate samples were collected at regular intervals of
time for determination of total hardness analysis with a FF-
2 HACH test kit by titration method. Column studies were
terminated when the column reached exhaustion. The
breakthrough curve for the column was determined by
plotting the ratio of the Ct/C0 (Ct and C0 are the hardness
concentration of effluent and influent, respectively) against
the time.
Experimental parameters of breakthrough curves
There are several experimental parameters, which were
calculated for the column hardness sorption process
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(Singh et al. 2012). Total hardness sorption by the column the Thomas model for an adsorption column is as follows
at saturation, qtot (mg), was calculated as follows: (Reynolds and Richards 1996; Fu and Viraraghavan 2003):
ðC0  Csat Þ  ts  Qv Ct 1
qtot ¼ ¼ ðC0  Csat Þ  Vs ; ð7Þ ¼ h i; ð12Þ
1000 C0 1 þ exp kT ðq0 M  C0 V Þ
Qv
where ts, is the saturation time of the column (min), Qv is
the flow rate (ml min-1) and Vs is the total volume (L) of where kT is the Thomas rate constant (ml min-1 mg-1); q0
effluent stored till saturation, respectively. C0 is the total is the equilibrium hardness uptake per g of adsorbent
hardness concentration of influent (mg L-1) and Csat is the (mg g-1); M is the mass of clinoptilolite in the column (g);
effluent hardness concentration (mg L-1) at Vs, C0 is the influent hardness concentration (mg L-1); Ct is
respectively. the effluent hardness concentration (mg L-1) at time t; Qv
Total hardness sorption at saturation by per unit dry is the flow rate (ml min-1). The value of Ct/C0 is the ratio
weight of the clinoptilolite in the column, qs (mg g-1), was of effluent and influent hardness concentrations. The value
calculated using Eq. 8: of t is the flow time (min), t = V/Qv, V is the throughput
qtot volume of the SHW (L) at time t. The linearized form of
qs ¼ ; ð8Þ the Thomas model is as follows (Han et al. 2007):
M
 
where M is the total dry weight (g) of clinoptilolite packed C0 k T q0 m
ln 1 ¼  kT C0 t: ð13Þ
in the column. Percent removal of hardness (%HR) at Ct V
saturation of the column was calculated according to Eq. 9: The values of kT and q0 can be determined from a plot ln
qtot [(C0/Ct) - 1] against t at a given flow rate using linear
%HR ¼  100; ð9Þ
Htot least square regressive analysis or from a plot of Ct/C0
against t using non-linear regression analysis as the values
where Htot is the total amount of hardness (mg) supplied to
of Ct/C0 are within 0.05–0.95. For the non-linear form of
the column till saturation. Htot was calculated by Eq. 10:
the Thomas model, Eq. 12 can be converted to the simple
C0  Qv  ts format as follows:
Htot ¼ : ð10Þ
1000 Ct 1
 ; ð14Þ
The total hardness sorption at breakthrough, qtb (mg), C0 1 þ expðb  aVÞ
was calculated by the following equation:
where:
ðC0  Ctb Þ  tb  Qv
qtb ¼ ¼ ðC0  Ctb Þ  Vb ; ð11Þ kT C0
1000 a¼ ; ð15Þ
Qv
where Vb is the total volume (L) of effluent collected till
breakthrough and Ctb is hardness concentration (mg L-1) k T q0 M
b¼ : ð16Þ
of Vb at time tb. In the present study, breakthrough of Qv
hardness sorption was assumed to have reached when Therefore, if Qv, M y C0 are constants, Ct/C0 is a
effluent metal concentration reached 100 mg L-1 function of V. Once a and b are determinate, kT and q0 can
(Bibiano-Cruz 2009). The total hardness sorption at be calculated by the following equation derived from
breakthrough by per unit dry weight of clinoptilolite Eqs. 17 and 18:
granules packed in column, qb (mg g-1), was calculated by
dividing qtb by M. aQv
kT ¼ ; ð17Þ
C0
Theoretical modeling of breakthrough curves bQv
q0 ¼ : ð18Þ
kT M
Various mathematical models can be used to describe
fixed-bed adsorption. Among these the Thomas model
(1948) is often adopted to predict the adsorptive curve of Error analysis
breakthrough in fixed mode (Han et al. 2007). Thomas
solution is simple to use and is one of the most general and In recognition of the nature of the dynamic behavior of the
widely used methods in column performance theory. Thus, fixed-bed sorption column, it has been necessary to intro-
the breakthrough data obtained from the column studies duce several criteria for the quantification of different
were examined using this kinetic model. The expression of aspects of the Thomas model performance. The statistical

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criteria used in the quantitative evaluation indicate an
estimation of error between experimental and theoretical
values of Ct/C0 used for plotting breakthrough curves.
Hence, in this study the Nash–Sutcliffe coefficient (NS),
the root mean square error (RMSE), the mean absolute
error (MAE), and the residual bias (BIAS) were used to
confirm the best fit to remove hardness from water (Han
et al. 2007). The lower limit for MAE and RMSE is zero.
The maximum value for NS is one. Both NS and BIAS can
be negative. A large BIAS value represents the worst case
performance of the model, while a large RMSE value
shows how much the simulations overestimate or under-
estimate the measurements. The RMSE is more appropriate
to represent model performance than the MAE when the
error distribution is expected to be Gaussian. The NS
coefficient ranges from minus infinity to 1 with higher
values indicating better agreement.
Results and discussion
Laboratory batch studies are useful in obtaining and pro-
viding fundamental equilibrium adsorption and kinetic data
for potential adsorbents. The importance of obtaining iso-
therms and kinetics curves lies in developing a model
which accurately represents the results obtained and could
be used for design purposes. Moreover, the models applied
to describe the breakthrough behavior have a key role in
the scale-up procedure from laboratory experiments
through pilot plant to industrial scale.
Sorption isotherms
Adsorption isotherm is the most important information to
indicate how adsorbate molecules distribute between the
liquid phase and solid phase when adsorption process
reaches an equilibrium state. In this study, Langmuir and
Freundlich equations (Eqs. 2, 3) were used for predicting
sorption capacities (i.e., sorption isotherms) and also
additional information derived from the estimated param-
eters (i.e. sorption nature, surface heterogeneity, etc.). In
this context, the estimated values of the parameters
(Langmuir values qm and b and Freundlich values KF and
n) derived from these isotherms were calculated and are
displayed in Table 1, together with the corresponding
correlation coefficient.
As it is indicated in Fig. 2a, b, sorption isotherms for
removal hardness ions adsorbed onto NC and HC exhib-
ited differences in shape and in the amount retained.
However, both saturation capacities of adsorbents may
seem low because the SHW solution is unsaturated of
hardness ions. As pointed out by Ho et al. (2000), sorp-
tion processes may include ion exchange, chelation,
189
physical and chemical sorption, as well as heterogeneity
of the clinoptilolite surface and the wide range of pore
sizes and surface properties make an analysis of the
observed behavior complex.
Taking into consideration the values of the correlation
coefficient (r), it can be observed that their values are very
close for both equations. In spite of all this, Langmuir
equation gives better correlation (0.99 for NC and HC)
between the theoretical and experimental data than Fre-
undlich Eq. (0.97 for NC and 0.96 for HC) (Table 1). A
better fit of the experimental data for Langmuir equation
explain the heterogeneity of the clinoptilolite structure, so
the strength of the bond created between the surface and
the preferential removal of the hardness ions are not the
same for all sites. As a result, the simplifying of assump-
tions is a necessity in the analysis, accepting the limitations
resulting from it.
As presented in Table 1, the Langmuir adsorption
capacities (qm) on NC and HC forms were estimated to be
9.68 mg g-1 (NC) and 10.50 mg g-1 (HC), respectively.
The qm values in the Langmuir isotherm indicate the
monolayer adsorption capacity of the low cost absorbent
(clinoptilolite) for removal water hardness present in the
SHW solution. According to Langmuir equation (Eq. 2),
the results exhibited that the hardness ions shows a stronger
affinity for HC than for the NC. On the basis of this
explanation, suggested that the preferential removal of the
hardness ions occurs on a homogeneous surface by
monolayer adsorption. Similar observations have been
reported by Cinar and Beler-Baykal (2005) for the removal
of water harness ions by natural zeolites through ion
exchange treatment.
The Freundlich isotherm (Eq. 3) is an empirical model
and it is widely recommended due to its accuracy. This
fairly satisfactory empirical isotherm can be used for non
ideal sorption that involves heterogeneous sorption. It gives
more accurate results than the Langmuir isotherm for a
wide variety of heterogeneous adsorption system. This
isotherm was selected in the analysis, which would enable
better fitting of the experimental adsorption equilibrium
data. The magnitude of the exponent n in Freundlich iso-
therm gives an indication of the favorable nature of the
sorption hardness system. The n values (Table 1) obtained
were 1.98 for NC and 2.65 for HC, which represents a
range of beneficial adsorption between 1 \ n \ 10 for
several investigated systems (Meshko et al. 2001). Values
of n in the range of 1.1–1.4 reflects the linear trend of the
isotherm (Rivas et al. 2006). In the present study, since
n lies between 1 and 10 it indicates the physical adsorption
of hardness ions onto absorbent media. Nearly similar
results have been reported in the literature (Mittal et al.
2007; Liu et al. 2010) for Langmuir and Freundlich
models.
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Table 1 Parameters of the

Model Parameter Natural clinoptilolite Homoionic clinoptilolite
equilibrium isotherms to
determine clinoptilolite qm (mg g-1) 9.68 10.50
exchange capacity and kinetic
parameters of the first order and Langmuir b (L mg-1) 2.02 9 10-2 3.56 9 10-2
second order adsorption, and r 0.99 0.99
intraparticle diffusion rate KF (mg1-nLng-1) 7 9 10-4 1.5 9 10-3
constants
Freundlich n 1.98 2.65
r 0.97 0.96
k1 (h-1) 2.78 9 10-3 4.69 9 10-3
-1
Lagergren first order model qe (mg g ) 10.22 11.58
r 0.994 0.985
k2 (g mg-1 h-1) 2.13 9 10-4 4.20 9 10-4
Pseudo-second order model qe (mg g-1) 12.90 13.45
r 0.996 0.992
kd (mmol g-1 min-0.5) 0.260 0.231
Intraparticle Cd (mmol g-1) 0.982 3.899
r 0.93 0.95

Batch kinetics studies
Sorption kinetics is useful for selecting optimum opera-
tional conditions of water treatment facilities for full-scale
processes. Figure 3 depicts the effect of contact time for
the hardness adsorption (qt) on NC and HC in function of
the contact time. In the adsoption test, the rate of hardness
removal was relatively fast at the beginning due to the
greater availability of the clinoptilolite surface area at the
start of the experiment. For both NC and HC form the
hardness sorption shows a quickly tendency to reach
equilibrium starting at 6 h with a maximum percent
removal attained after about 12 h. It is evident from Fig. 3
that hardness sorption occurred in two steps, that is,
&62 % of sorption occurred within 6 h followed by a very
slow sorption between 12 and 24 h, that according to Dişli
(2010) can be attributed to diffusion process. After 18 h the
removal percentage remained relatively constant reaching
100 % at 24 h.
Lagergren and Ho’s models described the sorption
kinetics with similar r values: (0.994) for NC and slightly
lower value (0.985) for HC (Fig. 3). Nevertheless, both
models are capable of modeling the adsorption regardless
of the type and amount of clinoptilolite used, describing
adequately the kinetic data. The values of rate parameters
and correlation coefficient (r) have been obtained and listed
in Table 1. It is observed that the pseudo-second order
model yields a somewhat better fit than the Lagergren
model by comparing the results of correlation coefficients.
This suggests that this sorption system is not a first order
reaction and that the pseudo-second order model, based on
the assumption that the rate-limiting step may be chemical
sorption or chemisorption involving valency forces through
sharing or exchange of electrons between sorbent and
sorbate, provides the best correlation of the data (Ho and
McKay 1999). As a consequence, the kinetics of the pro-
cess indicates a decrease in the rate of sorption in the range
6–18 h to attain equilibrium conditions. This conclusion is
consistent with those studies demonstrating that the
pseudo-second-order kinetic model is reasonably good fit
of data over the entire adsorption process (Chen et al.
2010).
As discussed above, the preferential removal of the
water hardness ions on HC than on NC form, suggest that
this removal capability is favored by the sodium
homoionization which gives preference to different mech-
anisms involved in the adsorption process. Hence, for
investigated hardness ions sorption by NC and HC, the
plots qt versus t1/2 did not pass through the origin (Fig. 4)
suggesting that even though the adsorption process
involved intraparticle diffusion, it was not the only rate-
controlling step. In this regard, this can be attributed to the
concentration driving force, bulk concentration minus
surface liquid concentration, which decreases rapidly and
so its influence is usually limited to the early stages of
adsorption. The positive value of intercept Cd is indicative
of some degree of boundary layer control (Özcan and
Özcan 2004). In this study, as can be seen from Fig. 4 and
Table 1, it appears that the thickness of the boundary layer
for homoionic clinoptilolite is greater than for natural
clinoptilolite.
The multilinear shape of qt - t1/2 relationships indicates
that more than one process affects adsorption of divalent
ions. As can be seen from Fig. 4, plot qt versus t1/2 for
hardness ions has first sharper portion, which can be con-
sidered as an external surface adsorption or faster adsorp-
tion stage, followed by gradual adsorption where
intraparticle diffusion is rate controlled. After that, in the

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Sustain. Water Resour. Manag. (2016) 2:183–197
Fig. 2 Langmuir and (a)
Freundlich isotherms in batch
experiments for: a natural
clinoptilolite (NC) and
b homoionic clinoptilolite (HC)
(b)
final equilibrium stage the intraparticle diffusion starts to
slow down due to the low adsorbate concentration in
solution. Kumar et al. (2009) observed a similar behavior
for Cr(III) removal using an amine-based polymer, aniline–
formaldehyde condensate (AFC) coated on silica gel.
Column sorption studies
Breakthrough curves for hardness sorption
Breakthrough in column tests can be defined as the
amount of influent solution passing through the bed before
a maximum effluent concentration is reached (Ecken-
felder 2000; Zhou et al. 2004). The ratio C (total hardness
concentration in the SHW effluent)/C0 (hardness
191
concentration of the SHW influent) was plotted against
the volume of the SHW solution passed, and the top x axis
shows the time taken for passing the SHW solution
through the column.
Taking into consideration the above results, the break-
through volume and the time to sorption of hardness ions
on clinoptilolite is gradual, thus resulting in relatively slow
attainment of breakthrough. In this research, breakthrough
and exhaustion are defined as the phenomena when the
ratios of effluent-to-influent concentration are 5 and 95 %,
respectively (Zhou et al. 2004). Thus, the breakthrough
point (C/C0 B 5 %) for the NC was 10.42 L (12.5 min)
and 19.59 L (23.5 min) for HC, as well as the exhaustion
point (C/C0 B 95 %) for the NC was 140.52 L (168.5 min)
and 165.97 L (199 min) for HC.
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192 Sustain. Water Resour. Manag. (2016) 2:183–197

Fig. 3 Lagergren’s first order (a)

and Hós pseudo-second order
model plots for the batch
kinetics of hardness adsorption
on: a natural clinoptilolite (NC)
and b homoionic clinoptilolite
(HC)

(b)

A summary of the experimental parameters of the ion
exchange column packed with NC and HC for water
softening are presented in Table 2. In this context, for an
initial water hardness concentration (C0) of 240 mg L, a
clinoptilolite dry weight mass (M) of 1122.5 g and a flow
rate of 14.5 ml min-1, the breakthrough time (tb) and the
breaktrough volume (Vb) was higher for HC than for NC
form (*80 %, 22 vs. 12 min and 18 vs. 10 L). However,
differences between values of the saturation time (ts) and
the saturation volume (Vs) for the HC and the NC form was
only *5 % (199 vs. 188 min and 170 vs. 160 L). Thus, the
sorption at breakthrough (qtb) and the sorption at saturation
(qe) was *30 % higher for the HC in comparison with NC
(4.87 vs. 3.76 mg g-1 and 15.4 vs. 12 mg g-1). Conse-
quently, these values result in a capacity removal at satu-
ration (HR) for the NC of 33.1 and 42.5 % for HC form
(Table 2).
Considering the NC form, the sorption of hardness ions
by the clinoptilolite was faster than that for HC, thus
resulting in quick attainment of breakthrough and satura-
tion. The hardness sorption at breakthrough and at satura-
tion was greater for the HC because its homoionic form
provided better driving force in the ion exchange softening
process during continuous column run.

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Sustain. Water Resour. Manag. (2016) 2:183–197
Fig. 4 Intraparticle diffusion (a)
plots at different concentrations:
a natural clinoptilolite (NC) and
b homoionic clinoptilolite (HC)
(b)
Theoretical modeling of breakthrough curves
Based on the modeling of the ion exchange process, Fig. 5
outlines the experimental measurements (points), as well as
linear and nonlinear curves predicted for hardness sorption
by NC and clinoptilolite pretreated with NaCl (HC),
according to the fitted parameters of the Thomas model
presented in Table 3. In this study, the Thomas model was
used to fit the column data to obtain the Thomas rate
constant (kT) and the maximum solid phase concentration
(q0). The values of equilibrium uptake per gram of the
adsorbent (qe, mg g-1) from experimental parameters of
breakthrough curves were also listed in Table 2. Taking
into consideration the above results, the Thomas model
fitted well to the experimental points obtained for the
193
hardness sorption, considering the SHW solution and the
packed column reactor under different ion exchange media
pretreatment.
From Table 3, it can seen that the values of the Nash–
Sutcliffe coefficient (NS) ranged from 0.909 to 0.976 and
the root mean square error (RMSE) ranged between 0.050
and 0.097. In the same way, the mean absolute error (MAE)
ranged between 0.042 and 0.077 and the residual bias
(BIAS) varied from 0.019 to 0.078. Hence, the quantitative
evaluation between Ct/C0 and time as expressed in Eq. 12
was significant, showing that the nonlinear regressive
method was more effective in predicting the sorption
kinetics than linear method (Table 3). Similar results have
been reported by Han et al. (2007) in their comparative
analysis for metyhylene blue adsorption onto natural
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Table 2 Summary of the experimental parameters of the ion are roughly 9.68 and 10.50 mg g-1 for NC and HC (cal-
exchange column packed with natural and homoionic clinoptilolite culated using the Langmuir equation), respectively. Similar
for water softening
results were reported by Tor et al. (2009), Gupta et al.
Parametera Unit Clinoptilolite (2001) and Chen et al. (2011). There may be several rea-
Natural Homoionic sons for the observed discrepancies between the batch and
column systems. One likely reason may be that the NC and
C0 mg L 240 240 the HC may form aggregates in the columns that favor
Qv ml min-1 14.5 14.5 enhanced solid state diffusion relative to the batch tests
M g 1122.5 1122.5 (Lopez et al. 1998).
tb min 12 22 In this context, the results demonstrate that the adsorp-
Vb L 10 18 tion bed capacity increase with homoionic pretreatment of
ts h 188 199 clinoptilolite (Table 3). According to Han et al. (2007), this
Vs L 160 170 may be associated with an increase the driving force of
qtb mg g-1 3.76 4.87 mass transfer in the liquid film. Furthermore, hardness ions
qs mg g-1 12.0 15.4 are more strongly bound to clinoptilolite pretreated with
HR % 33.1 42.5 NaCl, compared to natural clinoptilolite, as well as to
a
C0 initial hardness solution concentration, SHW, Qv flow rate, M
increased distribution coefficients that are indicative for
clinoptilolite dry weight, tb breakthrough time, Vb breaktrough vol- more complete exchange process. In spite of all this, the
ume, ts saturation time, Vs saturation volume, qtb sorption at break- lower performance onto natural clinoptilolite can be com-
through, qs sorption at saturation, HR hardness removal at saturation pensated by its low cost so it is still considered as ideal
adsorbent to remove hardness ions for water softening
applications. Nonetheless, it should be noted, however, that
applied results may vary depending on local geochemistry,
zeolite. Moreover, to provide an additional test of the which essentially suggest the necessity to extent this
Thomas model equation, the total sorption capacity q0 approach in natural waters. Performance evaluation of ion
calculated from Eq. 18 and qe calculated from the area exchange process using a pilot testing for removal of
above the S curves up to the saturation point should be hardness from groundwater is underway and will be pre-
close to each other (Eq. 8). The agreement of q0 and qe sented elsewhere.
(Tables 2, 3) confirmed the applicability of the Thomas
model to the examined column system.
Although the linear and nonlinear methods are suit- Conclusions
able for predicting the dynamic behavior of the column
with respect to both natural and homoionic conditions, the Removal of hardness ions from aqueous solutions for
results demonstrate that the values of the constant kT and q0 purified water has been an area of substantial technological
obtained by nonlinear regression are not similarity with the interest. Various technologies have been adopted for water
linear transform values. As seen from Table 3 and Fig. 5, softening; however, in most alternatives high power con-
the value of equilibrium uptake per gram of adsorbent, q0, sumption and expenses are required for operation and
was higher for linearized model form onto NC maintenance of the equipment. In this research, a combined
(13.96 mg g-1) and HC (15.20 mg g-1), as compared to use of batch and column experiments were performed in
the non-linear form (NC, 11.30 mg g-1and HC, laboratory conditions through the ion exchange process,
14.90 mg g-1). Nevertheless, according to the previous evaluating the effectiveness of NC and sodium HC on the
section, the statistics indices of agreements from non-linear removal characteristics of divalent cations. All tests were
regressive method were higher than that linear regressive performed with a synthetic hard water (SHW), obtained
method. This behavior may be explained by the fact that with the same ionic concentrations of a karst spring.
the slope of the breakthrough curve for the linearized Therefore, on the base of the experimental results of this
method decreased with increasing time as compared to investigation, the following conclusions can be drawn:
nonlinear method, thereby resulting in a slightly steeper Results of adsorption experiments showed that the
slope for the non-linear method and reducing the adsorp- hardness ions exhibited high adsorption capacity toward
tion capacity. The steepness of curve is a measure of the clinoptilolite-rich rocks, a cationic exchange media. The
efficiency of column to reach saturation (Singh et al. 2012). experimental adsorption equilibrium data were best
In this study, higher sorption capacities are obtained described by the Langmuir isotherm model and the
from the column experiments than from the batch tests. adsorption kinetics can be successfully fitted to pseudo-
From Table 1, sorption capacities obtained from batch tests second-order kinetic model. The results of the intraparticle

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Sustain. Water Resour. Manag. (2016) 2:183–197 195

Fig. 5 Breakthrough curves for (a)

hardness sorption and ion
exchange processes in the
packed column: a comparison
of experimental points, linear
and nonlinear predicted curves
of the Thomas model for natural
clinoptilolite (NC) and
b comparison of experimental
points, linear and nonlinear
predicted curves of the Thomas
model for homoionic
clinoptilolite (HC)

(b)

diffusion model suggest intraparticle diffusion was not the
only rate-controlling step and indicated some degree of
boundary layer control in the process of this sorbate–sor-
bent system. As a result, batch adsorption experiments
have shown that the amount of adsorbed (qe) for the
Langmuir isotherm indicates a monolayer sorption capacity
of clinoptilolite, which indicates a stronger affinity for HC
(10.5 mg g-1) than for the NC form (9.68 mg g-1). The
values obtained are found to agree with the values reported
in the literature.
From the perspective of process modeling, the dynamic
behavior of a fixed-bed column is described in terms of
breakthrough curve. Thus, in the present study, linear and
non-linear methods were used to determine the model
parameters and a comparative analysis was made between
the linear and non-linear method in estimating the relative
parameters for the adsorption of water hardness onto
clinoptilolite. That is, it was observed that the statistics
indices of agreements from non-linear Thomas model were
better than that linear Thomas model. Nevertheless, the
slope of the breakthrough curve for the linearized method
decreased with increasing time as compared to non-linear
method, thereby resulting in a slightly steeper slope for the
non-linear method and reducing the adsorption capacity.
Based on the modeling of the ion exchange process, the
study also concludes that the non-linear method is slightly
more effective in predicting the performance of the selec-
tive removal efficiency of hardness ions.
Natural zeolites have been widely used in water treat-
ment and especially clinoptilolite, due to its low cost and
high abundance. It has large cation-exchange capacity and
is capable of removing large quantities of hardness ions
from water samples. By loading the surface of clinoptilolite
a homoionic pretreatment to sodium form, a total

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Table 3 Estimation of
Parameter Unit Thomas model
parameters for the Thomas
model through the ion exchange Non-linear Linearized
process in the column test at
different experimental Natural Homoionic Natural Homoionic
conditions
a 0.043 0.037 0.038 0.044
b 2.273 2.580 2.482 3.117
kT ml min-1 mg-1 2.59 9 10-3 2.23 9 10-3 2.29 9 10-3 2.65 9 10-3
q0 mg g-1 11.3 14.9 13.9 15.2
Nash (NS) (-) 0.970 0.976 0.909 0.953
RMSE (-) 0.056 0.050 0.097 0.071
MAE (-) 0.048 0.042 0.077 0.058
BIAS (-) 0.029 0.019 0.078 0.045
Nash = coefficient of efficiency. Optimal value = 1.0 (-? \ NS B 1.0)
RMSE = root mean square error. Optimal value = 0.0 (0.0 B RSME)
MAE = mean absolute Error. Optimal value = 0.0 (0.0 B MAE)
BIAS = residual BIAS. Optimal value = 0.0 (-? \ BIAS B ? ?)

improvement in adsorption capacity can be achieved. Thus,
the homoionic clinoptilolite system is capable of adsorbing
slightly more ionic concentrations than natural clinoptilo-
lite with simultaneous noticeable decrease in water hard-
ness. It may be concluded that clinoptilolite may be used as
a low cost, natural and abundant source for the removal of
the hardness ions and it may be an alternative to more
costly materials.
Acknowledgments The authors would like to acknowledge the
Ministère des Relations Internationales du Quebec, the Consejo
Nacional de Ciencia y Tecnologı́a (CONACyT B330.523), the
Universidad Autónoma del Estado de México (UAEM FE052 and
FE053), the Institut national de la recherche scientifique INRS-ETE,
and the Ministère d’Éducation du Québec for providing funding and
logistical support for this study. The authors are also grateful for the
technical support of the laboratory technicians from the Interamerican
Centre of Water Resources (CIRA) in Toluca Mexico.
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